CN105417530A - Large-scale preparation method of nitrogen-doped graphene - Google Patents
Large-scale preparation method of nitrogen-doped graphene Download PDFInfo
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- CN105417530A CN105417530A CN201510945417.XA CN201510945417A CN105417530A CN 105417530 A CN105417530 A CN 105417530A CN 201510945417 A CN201510945417 A CN 201510945417A CN 105417530 A CN105417530 A CN 105417530A
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- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention discloses a large-scale preparation method of nitrogen-doped graphene, belongs to the technical field of preparation of the nitrogen-doped graphene and aims to solve problems of incapability of realizing large-scale production, high cost, harsh preparation conditions and complex synthesis technologies of existing nitrogen-doped graphene preparation methods. The preparation method of the nitrogen-doped graphene comprises steps as follows: I, magnesium powder and carbon and nitrogen sources are mixed, and precursors are obtained; II, the precursors are placed in inert gas, then heated to the temperature of 700-1,400 DEG C at the heating rate of 2-50 DEG C/min, and then subjected to acid pickling, ultrasonic treatment, suction filtration and drying, and the nitrogen-doped graphene is obtained. According to the method, magnesium is used as a strong reducing agent, melamine and the like are used as the carbon and nitrogen sources, used raw materials are low in cost, only dilute acid is adopted during aftertreatment, the technology is simple, operation is convenient, besides, the production cycle of the method is short, in-situ doping of nitrogen can be realized, large-scale production is facilitated, and the prepared nitrogen-doped graphene has a few layers.
Description
Technical field
The invention belongs to nitrogen-doped graphene preparing technical field, be specifically related to a kind of method that nitrogen-doped graphene is prepared in mass-producing.
Background technology
Graphene be planar monolayer carbon atom combine closely formed bi-dimensional cellular lattice material.The multiple outstanding performance that atomic and electronic structures due to its uniqueness makes it show traditional material not have, as specific surface area, adjustable band gap, high electron mobility, impayable electricity, mechanics, the feature such as calorifics and optical property of super large.But Graphene does not have band gap and smooth surface and hinders the application of Graphene in inertia.Graphene nitrating then can be opened band gap and adjust the free carrier density that conduction type changes the electronic structure raising Graphene of Graphene, thus improves conductivity and the stability of Graphene.The method preparing nitrogen-doped graphene at present is mainly divided into direct synthesis method and post-treating method.Direct synthesis method comprises chemical Vapor deposition process, nitrogen plasma electric discharge, arc discharge method, segregation growth method etc., has preparation condition harshness, production cost is high, be difficult to realize the problems such as suitability for industrialized production.Post-treating method comprises thermal treatment, solvent-thermal method, plasma processing method etc., have higher to equipment requirements, synthesis technique is complicated, be difficult to realize the problems such as suitability for industrialized production.Therefore, find and a kind of there is the study hotspot that technique is simple, easy to operate, cheap, nitrogen-doped graphene preparation method that is that easily realize the advantages such as industrialization scale operation becomes this field.
Summary of the invention
The object of the invention is in order to solve the existing method preparing nitrogen-doped graphene cannot scale operation, cost is high, preparation condition is harsh, synthesis technique is complicated problem, and provide a kind of novel mass-producing to prepare the method for nitrogen-doped graphene.
The method that nitrogen-doped graphene is prepared in mass-producing of the present invention follows these steps to realize:
One, be 1:(0.5 ~ 100 by magnesium powder and carbon nitrogen source according to mass ratio) ratio mixing, obtain presoma;
Two, the presoma that step one obtains is placed in rare gas element, then be warming up to 700 DEG C ~ 1400 DEG C with the temperature rise rate of 2 ~ 50 DEG C/min, keep 1 ~ 20h, be cooled to after room temperature again through overpickling, supersound process, collect solid formation after suction filtration, dry and obtain nitrogen-doped graphene;
Carbon nitrogen source wherein described in step one is one or more the mixture in trimeric cyanamide, pyrroles, pyridine, pyrazine, pyridazine, pyrimidine, cytosine(Cyt), uridylic, thymus pyrimidine, purine.
Magnesium as a kind of strong reductant, can restore the carbon atom in carbon nitrogen source molecule and generate magnesium nitride, and the carbon atom obtained is become nitrogen-doped graphene with nitrogenous organic molecule primary reconstruction by strong reductant magnesium by the present invention.
The beneficial effect that the method for nitrogen-doped graphene is prepared in mass-producing of the present invention is: raw material used is carbon nitrogen source and magnesium powder; with low cost; and only use diluted acid during aftertreatment; technique is simple, easy to operate; in addition present method with short production cycle, can in-situ doped nitrogen, be easy to large-scale production; the nitrogen-doped graphene number of plies prepared is few, can be used for the every field such as lithium ion battery, ultracapacitor, electrocatalysis.
Accompanying drawing explanation
Fig. 1 is x-ray photoelectron power spectrum (XPS) figure of nitrogen-doped graphene prepared by embodiment one;
Fig. 2 is the N1s figure of the x-ray photoelectron power spectrum (XPS) of nitrogen-doped graphene prepared by embodiment one;
Fig. 3 is atomic force microscope (AFM) figure of nitrogen-doped graphene prepared by embodiment three;
Fig. 4 is the dimensioned drawing of nitrogen-doped graphene prepared by embodiment three;
Fig. 5 is the Raman spectrogram of Graphene prepared by embodiment one, two, three, four and five; Wherein a is nitrogen-doped graphene prepared by embodiment one; B is nitrogen-doped graphene prepared by embodiment two; C is nitrogen-doped graphene prepared by embodiment three; D is nitrogen-doped graphene prepared by embodiment four; E is nitrogen-doped graphene prepared by embodiment five.
Embodiment
Embodiment one: the method that nitrogen-doped graphene is prepared in present embodiment mass-producing follows these steps to implement:
One, be 1:(0.5 ~ 100 by magnesium powder and carbon nitrogen source according to mass ratio) ratio mixing, obtain presoma;
Two, the presoma that step one obtains is placed in rare gas element, then be warming up to 700 DEG C ~ 1400 DEG C with the temperature rise rate of 2 ~ 50 DEG C/min, keep 1 ~ 20h, be cooled to after room temperature again through overpickling, supersound process, collect solid formation after suction filtration, dry and obtain nitrogen-doped graphene;
Carbon nitrogen source wherein described in step one is one or more the mixture in trimeric cyanamide, pyrroles, pyridine, pyrazine, pyridazine, pyrimidine, cytosine(Cyt), uridylic, thymus pyrimidine, purine.
The preferred trimeric cyanamide of carbon nitrogen source described in present embodiment.Can by arbitrarily than mixing when carbon nitrogen source is mixture.
Embodiment two: magnesium powder and carbon nitrogen source are 1:(0.5 ~ 5 according to mass ratio unlike step one by present embodiment and embodiment one) ratio mixing.Other step and parameter identical with embodiment one.
Embodiment three: magnesium powder and carbon nitrogen source mix according to the ratio that mass ratio is 1:1 unlike step one by present embodiment and embodiment two.Other step and parameter identical with embodiment two.
Embodiment four: one of present embodiment and embodiment one to three are one in argon gas, helium or its mixed gas unlike the rare gas element described in step 2.Other step and parameter identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four are warming up to 700 DEG C ~ 1200 DEG C unlike step 2 with the temperature rise rate of 2 ~ 15 DEG C/min.Other step and parameter identical with one of embodiment one to four.
Embodiment six: present embodiment and embodiment five are warming up to 800 DEG C ~ 1200 DEG C unlike step 2 with the temperature rise rate of 5 DEG C/min.Other step and parameter identical with embodiment five.
Embodiment seven: one of present embodiment and embodiment one to six are warming up to 800 DEG C ~ 1200 DEG C unlike with the temperature rise rate of 2 ~ 10 DEG C/min, keeps 1 ~ 4h.Other step and parameter identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven are carry out pickling by the one in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or its mixing acid unlike step 2.Other step and parameter identical with one of embodiment one to seven.
Mixing acid described in present embodiment can be that two or more acid in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid are by any combination.
Embodiment nine: present embodiment and embodiment eight are 1mol/L unlike the concentration of described pickle solution.Other step and parameter identical with embodiment eight.
Embodiment ten: one of present embodiment and embodiment one to nine are carry out in the acid solution of 1mol/L unlike the supersound process described in step 2.Other step and parameter identical with one of embodiment one to nine.
Embodiment 11: one of present embodiment and embodiment one to ten are carried out at 120 DEG C of temperature unlike the oven dry described in step 2.Other step and parameter identical with one of embodiment one to ten.
Embodiment one: the method that nitrogen-doped graphene is prepared in the present embodiment mass-producing follows these steps to implement:
One, magnesium powder and trimeric cyanamide are mixed according to the ratio that mass ratio is 1:1, obtain presoma;
Two, the presoma that step one obtains is placed in rare gas element, then be warming up to 700 DEG C with the temperature rise rate of 5 DEG C/min, keep 2h, be cooled to after room temperature again through overpickling, supersound process, collect solid formation after suction filtration, dry at 120 DEG C and obtain nitrogen-doped graphene.
The present embodiment employing concentration is that the hydrochloric acid of 1mol/L carries out pickling.Productive rate is 3.5%
As illustrated in fig. 1 and 2, in the present embodiment, obtained sample is made up of carbon, nitrogen and oxygen element the XPS figure of product obtained by the present embodiment as can be seen from Figure 1, C1s93.72%, N1s0.84%, O1s5.44%.
Embodiment two: the method that nitrogen-doped graphene is prepared in the present embodiment mass-producing follows these steps to implement:
One, magnesium powder and trimeric cyanamide are mixed according to the ratio that mass ratio is 1:1, obtain presoma;
Two, the presoma that step one obtains is placed in rare gas element, then be warming up to 800 DEG C with the temperature rise rate of 5 DEG C/min, keep 2h, be cooled to after room temperature again through overpickling, supersound process, collect solid formation after suction filtration, obtain nitrogen-doped graphene 120 DEG C of oven dry.
The present embodiment employing concentration is that the hydrochloric acid of 1mol/L carries out pickling.
Embodiment three: the method that nitrogen-doped graphene is prepared in the present embodiment mass-producing follows these steps to implement:
One, magnesium powder and trimeric cyanamide are mixed according to the ratio that mass ratio is 1:1, obtain presoma;
Two, the presoma that step one obtains is placed in rare gas element, then be warming up to 900 DEG C with the temperature rise rate of 5 DEG C/min, keep 2h, be cooled to after room temperature again through overpickling, supersound process, collect solid formation after suction filtration, dry at 120 DEG C and obtain nitrogen-doped graphene.
The present embodiment employing concentration is that the hydrochloric acid of 1mol/L carries out pickling.
In the present embodiment, as shown in Figures 3 and 4, in the present embodiment, the thickness of obtained sample is 6nm to the AFM figure of obtained product as can be seen from Figure 4.
Embodiment four: the method that nitrogen-doped graphene is prepared in the present embodiment mass-producing follows these steps to implement:
One, magnesium powder and trimeric cyanamide are mixed according to the ratio that mass ratio is 1:1, obtain presoma;
Two, the presoma that step one obtains is placed in rare gas element, then be warming up to 1100 DEG C with the temperature rise rate of 5 DEG C/min, keep 2h, be cooled to after room temperature again through overpickling, supersound process, collect solid formation after suction filtration, dry at 120 DEG C and obtain nitrogen-doped graphene.
The present embodiment employing concentration is that the hydrochloric acid of 1mol/L carries out pickling.
Embodiment five: the method that nitrogen-doped graphene is prepared in the present embodiment mass-producing follows these steps to implement:
One, magnesium powder and trimeric cyanamide are mixed according to the ratio that mass ratio is 1:1, obtain presoma;
Two, the presoma that step one obtains is placed in rare gas element, then be warming up to 1200 DEG C with the temperature rise rate of 5 DEG C/min, keep 2h, be cooled to after room temperature again through overpickling, supersound process, collect solid formation after suction filtration, dry at 120 DEG C and obtain nitrogen-doped graphene.
The present embodiment employing concentration is that the hydrochloric acid of 1mol/L carries out pickling.
As shown in Figure 5, a is Graphene prepared by embodiment one to the Raman spectrogram of nitrogen-doped graphene prepared by embodiment one, two, three, four and five; B is Graphene prepared by embodiment two; C is Graphene prepared by embodiment three; D is Graphene prepared by embodiment four; E is Graphene prepared by embodiment five; As can be seen from the figure D peak, G peak and 2D peak, illustrate that embodiment one, two, three, four and fifty percent merit prepares Graphene, and pass through the ratio at 2D peak and G peak, demonstrates out the obtained Graphene number of plies less.
Claims (10)
1. a method for nitrogen-doped graphene is prepared in mass-producing, it is characterized in that following these steps to realize:
One, be 1:(0.5 ~ 100 by magnesium powder and carbon nitrogen source according to mass ratio) ratio mixing, obtain presoma;
Two, the presoma that step one obtains is placed in rare gas element, then be warming up to 700 DEG C ~ 1400 DEG C with the temperature rise rate of 2 ~ 50 DEG C/min, keep 1 ~ 20h, be cooled to after room temperature again through overpickling, supersound process, collect solid formation after suction filtration, dry and obtain nitrogen-doped graphene;
Carbon nitrogen source wherein described in step one is one or more the mixture in trimeric cyanamide, pyrroles, pyridine, pyrazine, pyridazine, pyrimidine, cytosine(Cyt), uridylic, thymus pyrimidine, purine.
2. the method for nitrogen-doped graphene is prepared in a kind of mass-producing according to claim 1, it is characterized in that magnesium powder and carbon nitrogen source are 1:(0.5 ~ 5 according to mass ratio by step one) ratio mixing.
3. the method for nitrogen-doped graphene is prepared in a kind of mass-producing according to claim 2, it is characterized in that magnesium powder and carbon nitrogen source mix according to the ratio that mass ratio is 1:1 by step one.
4. the method for nitrogen-doped graphene is prepared in a kind of mass-producing according to claim 1, and the rare gas element that it is characterized in that described in step 2 is one in argon gas, helium or its mixed gas.
5. the method for nitrogen-doped graphene is prepared in a kind of mass-producing according to claim 1, it is characterized in that step 2 is warming up to 700 DEG C ~ 1200 DEG C with the temperature rise rate of 2 ~ 15 DEG C/min.
6. the method for nitrogen-doped graphene is prepared in a kind of mass-producing according to claim 5, it is characterized in that step 2 is warming up to 800 DEG C ~ 1200 DEG C with the temperature rise rate of 5 DEG C/min.
7. the method for nitrogen-doped graphene is prepared in a kind of mass-producing according to claim 1, it is characterized in that step 2 is warming up to 800 DEG C ~ 1200 DEG C with the temperature rise rate of 2 ~ 10 DEG C/min, keeps 1 ~ 4h.
8. the method for nitrogen-doped graphene is prepared in a kind of mass-producing according to claim 1, it is characterized in that step 2 carries out pickling by the one in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or its mixing acid.
9. the method for nitrogen-doped graphene is prepared in a kind of mass-producing according to claim 8, it is characterized in that the concentration of described pickle solution is 1mol/L.
10. the method for nitrogen-doped graphene is prepared in a kind of mass-producing according to claim 1, it is characterized in that the oven dry described in step 2 is carried out at 120 DEG C of temperature.
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| CN110562961A (en) * | 2019-08-26 | 2019-12-13 | 广西大学 | Method for in-situ synthesis of nitrogen and sulfur co-doped stereo graphene |
| CN114195128A (en) * | 2021-11-26 | 2022-03-18 | 北方民族大学 | Nitrogen-oxygen co-doped carbon nanosheet, preparation method and application thereof, and supercapacitor |
| CN115285979A (en) * | 2022-07-29 | 2022-11-04 | 中国人民解放军军事科学院防化研究院 | Preparation method of pyrrole nitrogen-doped graphene |
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| CN114195128A (en) * | 2021-11-26 | 2022-03-18 | 北方民族大学 | Nitrogen-oxygen co-doped carbon nanosheet, preparation method and application thereof, and supercapacitor |
| CN114195128B (en) * | 2021-11-26 | 2023-03-10 | 北方民族大学 | Nitrogen-oxygen co-doped carbon nanosheet, preparation method and application thereof, and supercapacitor |
| CN115285979A (en) * | 2022-07-29 | 2022-11-04 | 中国人民解放军军事科学院防化研究院 | Preparation method of pyrrole nitrogen-doped graphene |
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